Nguyen Thi Phuong Thu, Barroca-Aubry Nadine, Aymes-Chodur Caroline, Dragoe Diana, Pembouong Gaëlle, Roger Philippe
Institut de Chimie Moléculaire et des Matériaux d'Orsay (ICMMO), UMR 8182, Université Paris-Saclay, CNRS, 91405 Orsay, France.
Equipe Chimie des Polymères, Institut Parisien de Chimie Moléculaire, Sorbonne Université, CNRS, 4 Place Jussieu, 75005 Paris, France.
Molecules. 2022 Oct 12;27(20):6827. doi: 10.3390/molecules27206827.
Copolymers with two distinguished reactive repeating units are of great interest, as such copolymers might open the possibility of obtaining selective and/or consequent copolymers with different chemical structures and properties. In the present work, copolymers based on two active esters (pentafluorophenyl methacrylate and -nitrophenyl methacrylate) with varied compositions were synthesized by Cu(0)-mediated reversible deactivation radical polymerization. This polymerization technique allows the preparation of copolymers with high to quantitative conversion of both comonomers, with moderate control over dispersity ( = 1.3-1.7). Additionally, by in-depth study on the composition of each copolymer by various techniques including elemental analysis, NMR, FT-IR, and XPS, it was possible to confirm the coherence between expected and obtained composition. Thermal analyses by DSC and TGA were implemented to investigate the relation between copolymers' composition and their thermal properties. Finally, an evaluation of the difference in reactivity of the two monomer moieties was confirmed by post-modification of copolymers with a primary amine and a primary alcohol as the model.
具有两种不同反应性重复单元的共聚物备受关注，因为这类共聚物可能为获得具有不同化学结构和性质的选择性和/或连续共聚物提供可能性。在本工作中，通过铜（0）介导的可逆失活自由基聚合反应合成了基于两种活性酯（甲基丙烯酸五氟苯酯和甲基丙烯酸对硝基苯酯）且组成不同的共聚物。这种聚合技术能够制备出两种共聚单体转化率高至定量的共聚物，对分散度有适度控制（分散度 = 1.3 - 1.7）。此外，通过元素分析、核磁共振、傅里叶变换红外光谱和X射线光电子能谱等多种技术对每种共聚物的组成进行深入研究，得以证实预期组成与所得组成之间的一致性。通过差示扫描量热法和热重分析法进行热分析，以研究共聚物组成与其热性能之间的关系。最后，以伯胺和伯醇为模型对共聚物进行后修饰，证实了两种单体部分反应活性的差异。
